Hydrocarbon soluble catalyst supports and resultant polymerization catalysts

ABSTRACT

A method is provided for preparing hydrocarbon soluble magnesium siloxide supports comprising contacting such supports with sufficient aluminum alkoxide or organic ethers to render the supports hydrocarbon soluble. Thereafter the supports are contacted with a transition metal compound and halogenated to obtain polymerization catalysts.

This is a continuation in part, of application Ser. No. 429,387 filedSept. 30, 1982 and now abandoned.

This invention relates to hydrocarbon soluble magnesium and siliconcontaining supports for olefin polymerization catalysts. Morespecifically, this invention relates to a method of preparing suchsupports utilizing aluminum alkoxides or organic ethers as solubilizingagents and to a method of preparing catalysts from these hydrocarbonsoluble supports.

The art recognizes that active olefin polymerization catalysts can bemade by supporting a titanium chloride species on a magnesium halidealkoxide or oxide species. In some cases suitable electron donatingcompounds have been used in such synthesis. Many of these procedureshave suffered from being either lengthy or complex and further requireextensive washings of the catalyst. These extensive washings are oftennecessary to obtain acceptable catalyst efficiency and are tedious andexpensive.

Representative but non-exhaustive of the art dealing with magnesiumcontaining olefin polymerization catalysts is U.S. Pat. No. 4,223,118,which describes a polymerization catalyst in which a titanium halide isreacted with a magnesium siloxide in the presence of an aluminumalkoxide. U.S. Pat. No. 4,027,089 is representative of a group ofpatents in which magnesium aluminum complexes containing alkoxy orsiloxy groups are used to prepare polymerization catalysts. Thesereferences require that the alkoxy or siloxy ratios, when compared tothe aluminum plus magnesium ratios, be below about 0.8, a titaniumcompound having at least one halogen atom. The examples show catalystsprepared at Cl/Mg atomis ratios of 5-10 yielding a narrow molecularweight distribution polyethylene. U.S. Pat. Nos. 4,330,646; 4,330,647;4330,651; 4,335,229 describe polymerization catalysts having mole ratiosof alkoxy plus siloxy to magnesium plus aluminum less than 2.0. U.S.Pat. No. 4,218,339 describes polymerization catalysts prepared byreacting the reaction product of an alkyl magnesium chloride andpolymethylhydridosiloxane with tetra-n-butyltitanate and silicontetrachloride. Highest catalytic activity in this reference is shown inExample 20. The reference describes various halogenating agents whichare useful, but does not include the use of aluminum compoundscontaining chloride.

U.S. Pat. No. 3,907,759 teaches a magnesium chloride siloxide dissolvedin an aromatic hydrocarbon such as toluene and containing about 0.4moles of tetrahydrofuran per mole of magnesium. This reference alsodescribes a reaction product of a hydropolysiloxane such aspolymethylhydridosiloxane and a Grignard reagent such as adihydrocarbomagnesium containing up to 1.5 moles of tetrahydrofuran permole of magnesium as insoluble in n-heptane or n-hexane.

The bulk of these catalysts have an insoluble and a soluble portionwhich have to be separated after the catalyst preparation is complete.The insoluble portion alone is an acceptable catalyst. However, duringcatalyst preparation it is preferred that the catalyst components besoluble until the final catalyst is obtained. Solubility of thesematerials until the final preparation step would lead to better particlesize distribution. This produces a polymer powder from a slurrypolymerization process having better polymer powder flowability, polymerpowder transfer and better drying of the polymer powder in the variousprocess steps of commercial facilities.

It is also easier to carry out a catalyst preparation in a productionplant if the catalyst components are liquids or solutions and can bestored in non-agitated vessels and transferred to other vessels by meansof pumps without having to consider the settling rates of suspendedsolids or transferring of solids under an inert atmosphere.

It would therefore be of great benefit to provide a method of makingsoluble catalyst supports which provide high activity finishedcatalysts.

It is therefore an object of the present invention to provide a methodfor preparing hydrocarbon soluble magnesium and silicon containingsupports. It is a further object of the present invention to provide amethod for making catalysts from such supports. Other objects willbecome apparent to those skilled in this art as the descriptionproceeds.

I have now discovered that olefin polymerization catalyst supportshaving the general formula ##STR1## can be prepared in a hydrocarbonsoluble form by contacting these materials with aluminum alkoxideshaving the general formula

    Al(Q).sub.3

or organic ethers having the formula

    R.sup.2 --O--R.sup.3

wherein each Q can be R¹ or OR¹, but at least one Q must be OR¹ andwherein the organic ethers can optionally have mutually covalent bondsbetween R² and R³ to form cyclic ethers, and wherein R, R¹, R², and R³are, independently, alkyl groups containing from 1 to 20 carbon atoms,aryl, aralkyl, and alkaryl groups, each containing from 6 to 20 carbonatoms, and wherein R can, in addition, be hydrogen or alkoxy groupscontaining from 1 to 20 carbon atoms, and wherein a is 0 or 1 and n is 0or greater than 0. Generally, n will range from about 0.05 to about 100.Mixtures of alkoxides and ethers can be used.

Magnesium silicon supports wherein a is 0, and n is 0 are described inU.S. Pat. No. 4,374,755. However, these materials contain hydrocarboninsoluble species and are utilized in catalyst formation by contactingthese materials with titanium halides to form a precipitate which actsas an active catalyst.

In the process of the present invention, active catalysts are preparedby contacting solublized material with a non-halide transition metalalkoxide having at least one of the general formulas

    MO.sub.g (OR.sup.4).sub.n

or

    R.sup.4 O[M(OR.sup.4).sub.2 O].sub.p R.sup.4

or

    R.sup.4.sub.x M(OR.sup.4).sub.y

wherein M is titanium, vanadium, chromium, or zirconium, and R⁴ is analkyl group containing from 1 to 20 carbon atoms, aryl groups, alkarylgroups and aralkyl groups, each containing from 6 to 20 carbon atoms, gis 0 or 1, r is 2 to 4 and 2g+r is equal to the valence of M; p is atleast 2; and x+y is equal to the valence of M.

Once the solubilized magnesium silicon supports have been contacted withthe non-halide transition metal alkoxides, the resulting solution isreacted with a halogenating agent to obtain a polymerization catalysthaving a halogen to magnesium ratio of at least 2.0.

Representative but non-exhaustive examples of magnesium and siliconmaterials which are useful in the present invention when n=0 aretrimethylhydroxysilane, triethylhydroxysilane, triphenylhydroxysilane,methyldiphenylhydroxysilane, benzyldiphenylhydroxysilane,diethyldihydroxysilane, dipropyldihydroxysilane, dialkyldihydroxysilane,dicyclohexyldihydroxysilane, diphenyldihydroxysilane,butyltrihydroxysilane and phenyltrihydroxysilane.

Representative but non-exhaustive examples of these materials when (n)can be greater than 0 are polymethylhydrosiloxane (PMHS),polyethylhydrosiloxane, polymethylhydridodimethylsiloxane copolymer,polymethylhydromethyloctylsiloxane copolymer, polyethoxyhydrosiloxane,tetramethyldisiloxane, diphenyldisiloxane, trimethylcyclotrisiloxane,tetramethylcyclotetrasiloxane, polyphenylhydrosiloxane,polychlorophenylhydrosiloxane. These polymeric silicon compounds can bebound to magnesium, be present in the catalyst as free polymers, orboth.

When a polymeric compound such as polymethyl hydrosiloxane is reactedwith a dialkylmagnesium, a magnesium siloxide of the formula ##STR2##where n is greater than 1 is formed initially when dialkylmagnesium ispresent at low levels compared with the PHMS. This species can thenreact with additional alkylmagnesium to ultimately produce magnesiumsiloxide supports where n equals 0.

Representative but non-exhaustive examples of the aluminum alkoxides oralkyl aluminum alkoxides of the present invention are diethylaluminumethoxide, aluminum isopropoxide, aluminum n-propoxide, aluminummethoxide, aluminum sec-butoxide, aluminum decoxide, diethylaluminumphenoxide and aluminum growth product produced in Ziegler alcoholprocesses, whereas the oxidized growth product is prepared by oxidationof aluminum alkyls with oxygen or air. The aluminum alkoxides may beprepared in-situ by reacting an alcohol with a trialkylaluminum as isknown in the art.

Representative but non-exhaustive examples of organic ethers useful insolubilizing the materials of the present invention are tetrahydrofuran,diethylether, dibutyl ether, dioxane, diamyl ether, anisol, dipropylether, phenyl ethyl ether, or mixtures thereof.

Representative but non-exhaustive examples of the non-halide transitionmetal alkoxides of the present invention are tetraisopropyltitanate,tetra-n-butyltitanate, tetrabis (2-ethylhexyl)titanium, tri-n-butylvanadate, tetra-n-propylzirconate and tetra-n-butylzirconate, isopropyltitanate decamer, i.e. iso--C₃ H₇ --O(Ti(O--iso--C₃ H₇)₂ --O]₁₀ isoC₃H₇, butyl (triisopropoxy) titanium and mixtures thereof.

Representative but non-exhaustive examples of the halogenating agents ofthe present invention are ethylaluminum dichloride, diethylaluminumchloride, ethylaluminum sesquichloride, methyl and isobutyl analogues ofthese, tin tetrachloride, silicon tetrachloride, hydrogen chloride,trichlorosilane, aluminum chloride, ethylboron dichloride, boronchloride, diethylboron chloride, chloroform, phosphorous trichloride,phosphorous oxytrichloride, acetyl chlorides, thionyl chloride, sulfurchloride, methyl trichlorosilane, dimethyl dichlorosilane, titaniumtetrachloride, vanadium oxytrichloride, and vanadium tetrachloride.

Transition metal halide halogenating agents are not as preferred asnon-transition metal halides for the purpose of the present invention.It appears that the transition metal halides provide an excess oftransition metal to the reaction, which transition metal is not fullyreduced and thus decreases catalytic activity. However, these materialsare operable in the present invention. Most preferred halogenatingagents are chlorinating agents and of these diethylaluminum chloride,ethylaluminum dichloride ethylaluminum sesquichloride and methyl andisobutyl analogues of these are preferred.

In addition, it has been discovered that reaction of a titanium halidewith the hydrocarbon soluble magnesium siloxide described in the presentinvention produces solid catalysts which are high efficiency catalystsfor the polymerization of ethylene. Also it has been discovered thattreatment of a mixture of a titanium halide compound and the magnesiumsiloxides of this invention with an optimal halogenating agent from thepreviously listed compounds will greatly improve the catalyst efficiencybased on grams of polyethylene per gram of titanium. While theoreticalin nature, and I do not wish to be bound, I believe improved efficiencyoccurs because the Mg/Ti atomic ratio and the Cl/Mg atomic ratios areoptimized independently of each other. If the titanium compound is usedas the source for both the halogen and the titanium, then a reducedcatalyst efficiency is obtained.

Solubilizing agents can be added before, during or after formation ofthe magnesium silicon compounds. These materials can be formed in-situfor example as when trialkyl aluminum or magnesium alkyl/aluminum alkylmixture together with an alcohol are used. Most preferred solubilizingagents are those containing alkyl groups having from 1 to 8 carbon atomssuch that the aluminum alkoxides or organic ethers which can complex themagnesium silicon compound without steric hinderance.

For the purposes of the present invention the term "hydrocarbonsolubility" means solubility in saturated aliphatic hydrocarbons.Specifically, solubility can be determined as capability when forming asolution with n-hexane at 25° C. at a concentration of at least 0.01molar. Representative but non-exhaustive examples of saturatedhydrocarbons are n-heptane, n-hexane, cyclohexane, isononane, isohexane,cycloalkane, low-polynuclear aromatic solvent isooctane, isopentane,isobutane, pentane, butane and the like.

The catalysts of the present invention are useful in both solution andslurry polymerization. However, the catalysts must be treateddifferently and will provide different effects when used in a slurry ascompared to solution polymerization system.

In slurry polymerization systems I have found that altering the halogento magnesium ratio alters the molecular weight distribution. Forexample, changing the halogen as represented by the chlorine tomagnesium ratio from a 4:1 to 8:1 respectively broadens the molecularweight distribution of the polymer. It is preferred that the ratio ofhalogen, preferably chlorine to magnesium range from about 3:1 to about16:1 respectively. I have found that the activity tends to increase andthen decrease as the ratio of chlorine to magnesium is increased.However, I have also found that the molecular weight distribution ofpolymer produced using these catalysts tends to broaden as the halogento magnesium atomic ratio is increased from 4:1 to 8:1 respectively (4to 8 when magnesium is regarded as a constant 1). An atomic ratio in therange of about 6:1 to about 10:1 halogen to magnesium is most preferredfor a broad molecular weight distribution polymer.

While the chlorine to magnesium ratio affects molecular weightdistribution in slurry systems, it has been surprisingly found that thepolymer molecular weight distribution is little affected in solutionpolymerization systems. However, the catalyst activity has a maximumpossible value over a range of specific Cl/Mg ratios. The surprisingreversal of effect on efficiency and molecular weight distributionbetween solution and slurry polymerization systems has not beenexplained, but definitely exists. This result can be seen by anexamination of Examples 15 to 21 as compared to Example 23.

The catalysts of the present invention provide narrow and broadmolecular weight distributions in the obtained polymer. The molecularweight distribution in slurry polymerization systems can be altered bythe variation of Cl/Mg atomic ratio in catalyst based on Mg supports,whether soluble or insoluble. This effect is seen only when excesschloride is added using an aluminum-containing compound or aboron-containing compound, since both general types of compounds havesimilar function and behave similarly. This effect is not seen undersolution polymerization conditions.

When a silicon compound such as silicon tetrachloride is used as thehalogenating agent, a narrow molecular weight distribution polymer isproduced even at high Cl/Mg atomic ratios. Replacing the halogenatingagent with a tin halide such as tin tetrachloride results in a polymerhaving only a marginally broadened molecular weight distribution at highCl/Mg atomic ratios.

In carrying out a slurry polymerization the magnesium to titanium ratioshould be at least 1:1, and generally range from about 1:1 to about 50:1respectively, while the preferred range is from about 5:1 to about 25:1respectively. Note should be taken that in slurry polymerization systemsas the magnesium to titanium atomic ratio increases, polymer bulkdensity goes down while catalyst efficiency (grams of polymer per gramof transition metal) increases. It is therefore apparent to thoseskilled in this art that a balance between catalyst efficiency andpolymer bulk density must be obtained.

The catalyst of the present invention for use in both slurry andsolution systems, is prepared so that the silicon to magnesium molarratio is such that substantially all of the magnesium alkyl is convertedto magnesium siloxides. It should be noted that an excess of somesilicon compounds such as polymethylhydridosiloxane is not detrimentalexcept to catalyst cost and, in fact, sometimes has advantages such asin slurry powder bulk densities. The silicon to magnesium atomic ratiomust be at least 2:1 but can be much higher, the excess silicon beingfree silicon polymers as described in the present specification, or apolymeric siloxide bound to the magnesium. In addition, catalystefficiency in slurry polymerization is affected by the Si/Mg atomicratio. The preferred atomic ratio for optimum catalyst efficiency is atleast 2.0/1.0 (Si/Mg) to about 4.0/1.0 (Si/Mg). Lower atomic ratios aredetrimental to catalyst efficiency and higher ratios show no significantimprovement.

In solution polymerization systems, magnesium to titanium atomic ratiosshould be at least 1:1, and should range from about 5:1 to about 200:1respectively, but the most preferred range is from about 10:1 to about100:1. As the atomic ratio of magnesium to titanium increases, catalystefficiency increases, however along with this catalyst efficiencyincrease is found an increase in catalyst residues associated withmagnesium. Most notable of such residues are chloride ions. Thereforethose skilled in the art will realize that the magnesium to titaniumratio must be selected to compromise between chloride and titaniumlevels in the polyethylene obtained, since chloride levels which are toohigh provide a corrosive polyethylene, and in contrast low titaniumlevels are required for color-free or white polyethylene.

The catalysts of the present invention are activated with a co-catalystas is known in the art for Ziegler/Natta catalysts. The co-catalysts oftitanium ratio ranges from about 1 to 10,000, preferably from 1 to2,000. Typically, the co-catalyst is an aluminum alkyl. Representativebut non-exhaustive examples of aluminum alkyl useful as co-catalysts arethose having the formula Al(R²)₃ wherein R² denotes alkyl groupscontaining from 1 to 20 carbon atoms, hydrogen, halide or alkoxide, andat least one R² is alkyl and least two R² are alkyl, wherein one R² is ahalide or alkoxide.

High co-catalyst to catalyst ratios are preferred to scavengeimpurities. However, high ratios also have a detrimental effect in thatthe co-catalysts tend to over reduce the titanium and render thecatalyst less active. This lowering of activity is especially true insolution polymerization operated at high reaction temperatures.Co-catalysts such as aluminum alkyls are also known to solubilizemagnesium compounds at high temperatures with the result that undersolution conditions the catalyst support is erroded and dissolved by thehigh aluminum concentration. Therefore, in solution polymerization lowco-catalyst to catalyst ratios (preferably aluminum to titanium) areoften best. Under slurry polymerization conditions, higher aluminum totitanium ratios give better catalyst activity. In solution conditions,however, I have found that the reactions carried out at temperatures ator below about 150° C. the aluminum to titanium ratios should be high,paralleling slurry conditions. However, for reactions carried out aboveabout 220° C., the aluminum to titanium ratios should be adjusted lowerin order to obtain optimum catalyst efficiency (grams polyethylene pergram transition metal.

Preferred co-catalyst to catalyst mole ratios based on transition metalare therefore from about 10 to about 2000. These ratios range from about50 to 500 for slurry polymerization conditions. Under solutionpolymerization conditions, preferred co-catalyst to catalyst ratiosrange from about 10 to about 100.

In preparing the catalysts of the present invention, one of severalalternate procedures can be used. In one method the catalyst preparationis heated after the halogen ions are added. Temperatures of from about30° to about 150° C. and for times ranging from about 10 minutes toseveral hours. The catalyst can be heated for a sufficient time and thiswill vary widely since some halogen sources tend to react sluggishly.Heating thus improves this reaction as do length and contact times. In apreferred method, the components are simply mixed at temperatures offrom about 0° C. to about 100° C., preferably from about 10° C. to about40° C.

An alternate method of catalyst preparation requires decanting of thehydrocarbon solvent mixed with a soluble halogen (preferably chlorine)source after the chloride is added. However, this method provides noadvantage over the other method unless a large excess of the halogensource is added. Large excesses of halogen can reduce the chlorine orhalogen content of the polyethylene in solution polymerization andremoved reaction by-products.

Thus, these catalysts are useful in both solution polymerizations andslurry polymerization systems. In solution polymerization systems thecatalyst is useful at temperatures ranging from about 120° C. to about300° C. While in slurry polymerization conditions, the catalyst isuseful under conditions known to those skilled in this art, normallyabout 40° C. to about 90° C. and reactor pressures of 0 to 40,000 psig.The use of hydrogen to control molecular weight in either system isknown. These catalysts may generally be used in place of prior artcatalysts without modification.

The catalysts of the present invention will normally be effective whenresidence time parameters are observed. In slurry polymerization systemsthe residence time should range from about 30 minutes to about 10 hoursusually from about 1 to 5 hours, while in solution polymerizationsystems the residence time should range from about 10 seconds to severalhours, but usually from about 1 minute to about 1 hour.

These differences in residence times are due to polymerization rates andthermal deactivation of the catalyst in solution systems. Slurrypolymerization temperatures give lower polymerization rates butcatalysts are active for longer periods, so increased residence time canbe used to obtain good catalyst utilization. Solution polymerization incontrast has high polymerization rates but catalysts will thermallydeactivate such that the catalyst activity decreases rapidly with timeand usually becomes relatively inactive after about one hour.

The instant invention can be carried out in either continuous or batchpolymerization for commercial use continuous polymerizations arepreferred. Likewise, the polymerization reactor commonly is a tube or astirred tank reactor in common use, but any reactor can be utilizedwhich brings the ethylene and catalyst into contact.

Control of molecular weight can be done utilizing hydrogen as is knownin the art. In addition, molecular weight control can be controlled byreactor temperature or a combination of hydrogen and reactor temperaturein both slurry and solution. Normally, higher temperatures will reducemolecular weight, although this effect is seen more acutely in solutionpolymerization systems than in slurry polymerization systems.

The invention is more concretely described with reference to theexamples below wherein all parts and percentages are by weight unlessotherwise specified. The examples are provided to illustrate the presentinvention and not to limit it.

In the examples which follow, dibutyl magnesium obtained from theLithium Corporation of America is a solution in heptane.Polymethylhydridosiloxane (PMHS) was obtained from Petrarch Systems,Inc. Triethylaluminum (TEAL) and ethylaluminum dichloride (EADC) wereobtained from Texas Alkyls Inc. as solutions in hexane. ISOPAR® G is anisoparaffinic mixture of saturated hydrocarbons obtained from ExxonCompany, U.S.A. All other chemicals were reagent grade and used asreceived, except for hexane which was purified with molecular sieves andnitrogen purged to remove traces of oxygen and water.

Use of aluminum alkoxides as a solubilizing agent is set forth in theExamples below.

EXAMPLE 1

The reaction of RMgR, AlQ₃, alcohol and PMHS is illustrated.Seventy-five milliliters (ml) of a 2.0 molar n-propyl alcohol (150millimoles) solution in hexane was added slowly to a stirred solution of84.3 molar triethylaluminum (50 millimoles) and 140 ml of 0.715 molardibutylmagnesium (100 millimoles). Polymethylhydridosiloxane (PMHS, 12.8ml, 210 millimoles Si) was added and the resultant solution was heatedat 65°-75° C. for one hour. After cooling to room temperature, asolution was obtained.

EXAMPLE 2

The order of addition, AlQ₃, alcohol RMgR and PMHS wherein the ratio ofAlQ₃ to magnesium is 0.1 is illustrated.

Thirty milliliters of a 2.0 molar n-propyl alcohol (60 millimoles)solution in hexane was slowly added to a stirred solution of 33.7 ml of0.593 molar triethylaluminum (20 millimoles), followed by 280 ml of0.715 molar dibutylmagnesium (200 millimoles). Then, 12.8 mlpolymethylhydridosiloxane (210 millimoles Si) was added. After heatingthe stirred mixture for one hour at about 70° C., the solution wascooled to room temperature and diluted to 500 ml with hexane. Morepolymethylhydridosiloxane (12.8 ml, 210 millimoles Si) was added and thesolution heated to 80° C. for one-half hour. After cooling to roomtemperature, the solution was diluted to 500 ml with hexane to make upthe hexane lost in evaporation during the heating. After standing for 19days, this solution became a viscous gel.

EXAMPLE 3

The results of reacting only RMgR and PMHS is set forth as a comparison.Polymethylhydridosiloxane (13.4 ml 220 millimoles Si) was added to asolution of 100 ml hexane and 140 ml of 0.715 molar dibutylmagnesium. Anexothermic reaction took place and the mixture turned to a solid gel.

EXAMPLE 4

The reaction of AlQ₃, alcohol, RMgR and PMHS, wherein the aluminumalkoxide to magnesium ratio is 0.5 is illustrated. The procedure ofExample 2 was repeated exactly except using 169 ml of 0.593 molartriethylaluminum (100 millimoles) and 150 ml of 2.0 molar n-propylalcohol in hexane so that the Al(OR₃)/Mg ratio was increased to 0.5.After 19 days, the resultant solution was unchanged in physicalappearance.

EXAMPLE 5

The utility of the solubilized material of the present invention as apolymerization catalyst and was determined experimentally. Thesolubilized components of Example 1 were utilized.Polymethylhydridosiloxane (12.8 ml, 210 mmoles Si) was added to astirred solution of 33.7 ml of 0.593 molar triethylaluminum, 30.0 ml of2.0 molar n-propylalcohol in hexane, and 280 ml of 0.715 molardibutylmagnesium. The mixture was heated for one hour at about 70° C.Hexane was added to give a volume of about 500 ml and 12.8 ml ofpolymethylhydridosiloxane was added. The solution was heated to about80° C. for 1/2 hour and the volume adjusted to 500 ml. A portion of theabove solution (125 ml) was mixed with 2.0 ml of 1.0 molartetraisopropyltitanate in hexane. The solution was stirred and 87 ml of1,149 molar ethylaluminum dichloride was added dropwise in about 1/2hour. A portion of the catalyst slurry was diluted with hexane. Analiquot of this dilute catalyst containing 0.001 millimoles of titaniumwas added to a nitrogen purged, stirred, 1.8 liter reactor containing600 ml of dry, oxygen-free hexane and 1.7 ml of 0.593 molartriethylaluminum. The reactor was pressured to 50 psig with hydrogen andvented to 0 psig. The procedure was then repeated three more times. Thereactor pressure was adjusted to 30 psig with hydrogen and then 100 psigwith ethylene. The reactor contents were heated to 80° C. and thenethylene was added to maintain a constant reactor pressure of 150 psig.After one hour, the reactor was cooled and vented. The reactor contentswere filtered and the polyethylene dried in a vacuum oven at 70° C.until free of hexane. The polyethylene weighed 153.1 grams and had amelt index (ASTM 1238, condition E) of 1.3. The catalyst efficiency was3,200,000 grams of polyethylene per gram of titanium.

EXAMPLE 6

The catalyst preparation procedure of Example 5 was repeated except theamounts of aluminum alkoxide (triethylaluminum plus n-propyl alcohol)used for solubilization was increased so that the magnesium siloxidesolution had an Al(OR)₃ /Mg molar ratio of 2.

Using the above catalyst, the polymerization procedure of Example 5 wasrepeated using an aliquot of catalyst containing 0.005 millimoles oftitanium. The polyethylene produced weighed 2.5 grams. The catalystefficiency was 10,400 grams of polyethylene per gram of titanium.

EXAMPLE 7

An example was carried out to show the effect of organic ether whenpresent during the reaction of PMHS and RMgR. A solution of 140 mldibutylmagnesium (100 millimoles) and 4.1 ml THF (50 millimoles wasprepared at 50° C. and 13.4 ml of PMHS (200 millimoles) was added slowlyenough that the exotherm reaction did not heat the solution above about75° C. The mixture was held at 75° C. for one hour by heating with aheating mantel. After cooling to room temperature, a solution wasobtained.

EXAMPLE 8

An experiment was carried out to show the effect of an organic ether ona reaction product of RMgR and PMHS. PMHS (6.4 ml, 105 millimoles) wasadded to a stirred solution of 69.9 ml dibutylmagnesium (50 millimoles)and 130 ml hexane. In a few minutes, a solid gel had formed and themagnetic stir bar would no longer stir the mixture. THF (2.0 ml, 25millimoles) was added to the solid gel and the gel rapidly liquified.After mixing, a solution was obtained.

EXAMPLE 9

Experiments were carried out to determine the minimum amount of organicether required to solubilize the reaction product of RMgR and PMHS.

PMHS (6.4 ml, 105 millimoles) was added to a stirred solution of 69.9 mldibutylmagnesium (50 millimoles), and 130 ml hexane. The mixture washeated to 60°-70° C. for one hour. After cooling to room temperature, aslurry was obtained. THF at a THF/Mg ratio of 0.05 did not solubilizeall of the magnesium disiloxide. The procedure was repeated using 5.0 mlof a 1.0 molar THF in hexane solution. After cooling to room temperatureovernight, a viscous solution was obtained. A THF/Mg ratio of 0.10solubilized the magnesium disiloxide.

EXAMPLE 10

Utility of an organic ether solubilized RMgR and PMHS reaction productas a component in a polyolefin catalyst was determined experimentally.In this experiment, the solution of Example 6 was utilized together witha titanium halide.

A 1.0 molar solution (200 ml) of titanium tetrachloride (200 millimoles)in hexane was added dropwise to the stirred solution of Example 6. Thesolids were allowed to settle and the supernatant removed bydecantation. The solids were reslurried with fresh hexane and thedecantation procedure was repeated five more times to wash the solidfree of hexane soluble species.

A portion of the catalyst slurry was diluted with hexane. An aliquot ofthis dilute catalyst containing 0.02 millimoles of titanium was added toa nitrogen purged, stirred, 1.8 liter reactor containing 600 ml of dry,oxygen-free hexane and 3.4 ml of 0.593 molar triethylaluminum. Thereactor was pressured to 50 psig with hydrogen and vented to 0 psig.This procedure was then repeated three more times. The reactor pressurewas adjusted to 10 psig with hydrogen and then 100 psig with ethylene.The reactor contents were heated to 80° C. and then ethylene was addedto maintain a constant reactor pressure of 150 psig. After one hour, thereactor was cooled and vented. The reactor contents were filtered andthe polyethylene dried in a vacuum oven at 70° C. until free of hexane.The polyethylene weighed 270 grams and had a melt index (ASTM 1238,Condition E) of 0.43. The catalyst efficiency was 282,000 grams ofpolyethylene per gram of titanium.

EXAMPLE 11

The use of an ether followed by halogenation to produce an olefinpolymerization catalyst and resulting utility were illustrated.

Polymethylhydridosiloxane (13.4 ml, 220 mmoles Si) was slowly added to asitred solution of 140 ml of 0.715 molar dibutylmagnesium and 4.1 mltetrahydrofuran (50 mmoles). The solution temperature was maintained at70°-80° C. for one hour and then cooled to room temperature.Tetraisopropyltitanate (6.0 ml, 20 mmoles) was added to the stirredsolution followed by the dropwise addition of 175 ml of 1.149 molarethylaluminum dichloride (200 mmoles).

A portion of the catalyst slurry was diluted with hexane. An aliquot ofthis dilute catalyst containing 0.005 millimoles of titanium was addedto a nitrogen purged, stirred 1.8 liter reactor containing 600 ml ofdry, oxygen-free hexane and 1.7 ml of 0.593 molar triethylaluminum. Thereactor was pressured to 50 psig with hydrogen and vented to 0 psig. Theprocedure was repeated three additional times. The reactor pressure wasadjusted to 10 psig with hydrogen and then 100 psig with ethylene. Thereactor contents were heated to 80° C. and then ethylene was added tomaintain a constant reactor pressure of 150 psig. After one hour, thereactor was cooled and vented. The reactor contents were filtered andthe polyethylene dried in a vacuum oven at 70° C. until free of hexane.The polyethylene weighed 175.8 grams and had a melt index (ASTM 1238,condition E) of 0.26. The catalyst efficiency was 734,000 grams ofpolyethylene per gram of titanium.

EXAMPLE 12

Polymethylhydridosiloxane (64.1 ml, 1050 mmoles Si) was slowly added toa solution of 699 ml of 0.715 molar dibutylmagnesium (500 mmoles) and20.4 ml of tetrahydrofuran (250 mmoles). The temperature was maintainedat 70°-80° C. for 1 hour. The solution was cooled to room temperatureand diluted to 1.0 liter so that the magnesium siloxide concentrationwas 0.5 molar.

An aliquot (100 ml, 50 mmoles Mg) of the above solution was mixed with5.0 ml of 1.0 molar tetraisopropyltitanate (5.0 mmoles) in hexane. Tothis stirred solution was added 87 ml of 1.149 molar ethylaluminumdichloride (100 mmoles) dropwise.

An aliquot of this catalyst containing 0.001 millimoles of titanium wasused in the polymerization procedure of Example 10. The recoveredpolyethylene weighed 123.9 grams and had a melt index (ASTM 1238,condition E) of 0.23. The catalyst efficiency was 2,590,000 grams ofpolyethylene per gram of titanium.

EXAMPLE 13

The catalyst procedure of Example 11 was repeated except using 2.0 ml of1.0 molar tetraisopropyltitanate so that the catalyst had a Mg/Ti atomicratio of 25.

The polymerization procedure of Example 11 was repeated and 154.8 gramsof polyethylene was obtained. The polymer had a melt index (ASTM 1238,condition E) of 0.29. The catalyst efficiency was 3,230,000 grams ofpolyethylene per gram of titanium.

EXAMPLE 14

The copolymerization of ethylene and octene-1 to produce linear lowdensity polyethylene under solution polymerization conditions isillustrated.

A 0.387 molar solution of mixed aluminum alkoxides was prepared usingISOPAR® G. The mixed aluminum alkoxides were obtained by the controlledoxidation of a trialkylaluminum mixture in which the alkyl groups arelinear, saturated alkyl groups containing two to thirty carbon atoms andthe average being about 10 carbon atoms.

A 238.7 milliliter solution of the 0.387 molar mixed aluminum alkoxideswas added to 500 ml of 0.739 molar dibutylmagnesium. To this solutionwas slowly added 47.3 ml of polymethylhydridosiloxane so that thetemperature did not go over 70° C. The solution was heated for 1/2 hourat 70° C. and cooled to room temperature to give a magnesium siloxidesupport solution that was 0.465 molar in magnesium. A portion of thissupport solution was diluted to 0.1 molar with ISOPAR® G.

The polymerization catalyst is formed by mixing the followingingredients in the order given:

6.3 ml of 0.1 molar magnesium siloxide support solution 88.7 ml ofISOPAR® G

3.1 ml of 0.5 molar ethylaluminum dichloride

1.25 ml of 0.013 molar tetraisopropyltitanate

0.7 ml of 0.892 molar triethylaluminum in ISOPAR® G

A portion of the above catalyst containing 0.00163 millimoles oftitanium is pressured with nitrogen into a stirred 1.8 liter stainlesssteel reactor containing 1.0 liters of ISOPAR® G, about 5 psi hydrogen,150 psi ethylene, and 50 ml octene-1 at a temperature of 185° C. Thetotal reactor pressure is held constant by addition of ethylene. After30 minutes of reaction, the reactor content is dumped into a 3.0 literstainless steel resin kettle equipped with a reflux condensor. Thesolution is cooled to room temperature and the solvent removed. Thepolymer weight is 22.3 grams. The catalyst efficiency is 386,000 gramsof polymer per gram of titanium. The polymer melt index is 15.4 and thedensity is 0.9265 g/cc (ASTM D-1505 using ASTM D-1928 for the samplepreparation).

EXAMPLES 15 THROUGH 21

The effect of Cl/Mg atomic ratio upon catalyst efficiency wasillustrated.

(a) Support Solution Preparation

Aluminum sec-butoxide (47.0 ml, 185 millimoles Al) was added to 1000 mlof 0.739 molar dibutylmagnesium (739 millimoles Mg) contained in amagnetically stirred 1.2 liter flask fitted with a heating mantel. Tothe resultant solution was added 94.6 ml of polymethylhydridosiloxane(1552 millimoles Si) dropwise at a rate so that the temperature did notgo over about 70° C. The solution was then heated to maintain atemperature of about 70° C. for one-half hour. After cooling to roomtemperature the solution was analyzed for magnesium and a portiondiluted with ISOPAR® G to give a 0.1 molar support solution

(b) Catalyst Preparation

An aliquot of 0.5 molar ethylaluminum dichloride (EADC) in hexane wasadded to an ISOPAR® G support solution as prepared in section 1(a). Tothe resultant slurry was added aliquots of 0.01 molar Ti(OiPr)₄(tetraisopropyltitanate) and 0.898 molar TEAL (triethylaluminum) in thatorder to give a catalyst slurry which contained 0.0025 millimoles oftitanium per 10 ml of slurry. The exact volumes of reactants are listedin Table 1.

                                      TABLE 1                                     __________________________________________________________________________         ml of 0.1 m                                                                              ml of                                                                             ml of                                                                              ml of                                                Example                                                                            Support                                                                             ml of                                                                              0.5 m                                                                             0.01 m                                                                             0.989 m                                                                            Atomic Ratios                                   No.  Solution                                                                            Diluent                                                                            EADC                                                                              Ti(OiPr).sub.4                                                                     TEAL Cl/Mg                                                                             Mg/Ti                                                                             TEAL/Ti                                 __________________________________________________________________________    15   12.5  81.1 2.5 2.5  1.4  2.0 50  50                                      16   12.5  80.5 3.1 2.5  1.4  2.5 50  50                                      17   12.5  79.8 3.8 2.5  1.4  3.0 50  50                                      18   12.5  78.6 5.0 2.5  1.4  4.0 50  50                                      19   12.5  77.3 6.3 2.5  1.4  5.0 50  50                                      20   12.5  76.1 7.5 2.5  1.4  6.0 50  50                                      21   12.5  73.6 10.0                                                                              2.5  1.4  8.0 50  50                                      __________________________________________________________________________

Ethylene Polymerizations

An aliquot of each catalyst prepared as described in Table 1 waspressured with nitrogen into a stirred 1.8 liter stainless steel reactorcontaining 1.0 liters of ISOPAR® G, about 5 psi hydrogen, and 150 psiethylene at a temperature of 150° C. The total reactor pressure was heldconstant by addition of ethylene.

After 30 minutes of reaction, the reactor contents were dumped into a3.0 liter stainless steel resin kettle equipped with a reflux condensor.The solution was cooled to room temperature and the solvent removed. Theweights of solvent-free polymer and catalyst efficiencies are set out inTable 2.

                  TABLE 2                                                         ______________________________________                                               Milli-                                                                        moles                                                                  Catalyst                                                                             Tita-                   Catalyst                                       Example                                                                              nium    Cl/Mg   gPE     Efficiency                                                                            I.sub.10 I.sub.2                                                                   MI                                ______________________________________                                        15     .005    2.0     less than 2                                                                           less than                                                                             --   --                                                                8,000                                         16     .0025   2.5     21.42   179,000 7.8   0.165                            17     .0025   3.0     36.47   305,000 8.7  1.05                              18      .00125 4.0     37.95   634,000 7.6  2.11                              19      .00125 5.0     35.11   586,000 7.3  1.52                              20     .0025   6.0     33.57   280,000 7.7  1.25                              21     .0025   8.0     23.46   196,000 7.0   0.646                            ______________________________________                                         I.sub.10 I.sub.2 ratios were determined wherein I.sub.2 is the melt index     of ASTM 1238 condition E and I.sub.10 as a high load melt index (ASTM 123     condition N0 to give a ratio of 15.6. The higher the I.sub.10 I.sub.2         ratio, the broader the molecular weight distribution of the polymer.     

EXAMPLE 22

The use of an ether followed by halogenation to produce an olefinpolymerization catalyst and resulting utility were illustrated.

Polymethylhydridosiloxane (64.1 ml, 1050 mmoles Si) was slowly added toa stirred solution of 699 ml of 0.715 molar dibutylmagnesium and 20.4 mltetrahydrofuran (250 mmoles). The solution temperature was maintained atnot over 80° C. for one hour and then cooled to room temperature anddiluted to 1 liter. To 100 ml of this solution was added atetraisopropyltitanate solution (2.0 ml, 5 mmoles), followed by thedropwise addition of 87 ml of 1.149 molar ethylaluminum dichloride (100mmoles).

A portion of the catalyst slurry was diluted with hexane. An aliquot ofthis dilute catalyst containing 0.001 millimoles of titanium was addedto a nitrogen purged, stirred 1.8 liter reactor containing 600 ml ofdry, oxygen-free hexane and 1.7 ml of 0.593 molar triethylaluminum. Thereactor was pressured to 50 psig with hydrogen and vented to 0 psig. Theprocedure was repeated three additional times. The reactor pressure wasadjusted to 10 psig with hydrogen and then 100 psig with ethylene. Thereactor contents were heated to 80° C. and then ethylene was added tomaintain a constant reactor pressure of 150 psig. After one hour, thereactor was cooled and vented. The reactor contents were filtered andthe polyethylene dried in a vacuum oven at 70° C. until free of hexane.The polyethylene weighed 154.8 grams and had a melt index (ASTM 1238,condition E) of 0.29. The catalyst efficiency was 3,230,000 grams ofpolyethylene per gram of titanium.

EXAMPLE 23

The broadening of polymer molecular weight distribution by varying theCl/Mg atomic ratio is illustrated.

A. A 107.5 milliliter portion of the 0.465 molar magnesium siloxidesupport solution prepared in Example 14 was mixed with 18 ml of hexaneand 4.72 ml of 1.06 molar tetraisopropyltitanate in hexane. To theresultant solution was added dropwise, 87 ml of 1.149 molarethylaluminum dichloride to give a catalyst slurry having a Mg/Ti atomicratio of 10 and a Cl/Mg atomic ratio of 4.

B. The procedure of section (A) was repeated using 174 ml of 1.149 molarethylaluminum dichloride to give a catalyst slurry having a Mg/Ti atomicratio of 10 and a Cl/Mg atomic ratio of 8.

C. A portion of the catalyst slurry was diluted with hexane. An aliquotof this dilute catalyst containing 0.002 millimoles of titanium wasadded to a nitrogen purged, stirred, 1.8 liter reactor containing 600 mlof dry, oxygen-free hexane and 2.5 ml of 0.100 molar triethylaluminum.The reactor was pressured to 50 psig with hydrogen and vented to 0 psig.The procedure was then repeated three more times. The reactor pressurewas adjusted to 30 psig with hydrogen and then 100 psig with ethylene.The reactor contents were heated to 80° C. and then ethylene was addedto maintain a constant reactor pressure of 150 psig. After one hour, thereactor was cooled and vented. The reactor contents were filtered andthe polyethylene dried in a vacuum oven at 70° C. until free of hexane.The results are outlined in Table 3.

                  TABLE 3                                                         ______________________________________                                        Polymerization                                                                                      Catalyst Efficiency                                                                             Polymer                               Catalyst                                                                             Cl/Mg   gPE    Kg PE/gTi   I.sub.2                                                                             I.sub.10 I.sub.2                      ______________________________________                                        23-A   4       174.3  1,820       4.26   7.7                                  23-B   8       145.3  1,520       1.67  10.1                                  ______________________________________                                    

EXAMPLE 24

This example illustrates the importance of selecting the optimumcocatalyst/titanium molar ratio for the desired reactor temperature inorder to maximize the catalyst efficiency.

A. A catalyst slurry was prepared in which the cocatalyst(triethylaluminum)/Ti molar ratio was 25 by mixing the followingingredients in a magnetically stirred bottle in the order listed:

12.5 ml--0.1 molar support solution prepared in Example 15a

81.6 ml--ISOPAR® G

2.7 ml--1.149 molar ethylaluminum dichloride

2.5 ml--0.01 molar tetraisopropyltitanate in ISOPAR® G

0.7 ml--0.892 molar triethylaluminum

B. A catalyst slurry was prepared in which the cocatalyst/Ti molar ratiowas 100 by mixing the following ingredients in a magnetically stirredbottle in the order listed:

12.5 ml--0.1 molar support solution prepared in Example 15a

79.5 ml--ISOPAR® G

2.7 ml--1.149 molar ethylaluminum dichloride

2.5 ml--0.01 molar tetraisopropyltitanate in ISOPAR® G

2.8 ml--0.892 molar triethylaluminum

C. Six aliquots of the catalysts prepared in sections A and B werepressured with nitrogen into a stirred 1.8 liter stainless steel reactorcontaining 1.0 liters of ISOPAR® G, the psi hydrogen given in Table 4,and 140 psi ethylene at a temperature given in Table 4. The totalreactor pressure was held constant by addition of ethylene.

After 30 minutes of reaction, the reactor contents were dumped into a3.0 liter stainless steel resin kettle equipped with a reflux condensor.The solution was cooled to room temperature and the solvent removed. Thepolymer weights, catalyst efficiency, and polymer melt index (I₂) arelisted in Table 4.

                                      TABLE 4                                     __________________________________________________________________________              Approxi-                                                                           Milli-                                                                            Reactor                                                                            Cocatalyst                                                                             Catalyst                                          Example                                                                            mate moles                                                                             Temp.                                                                              Ti       Efficiency                                   Aliquot                                                                            No.  psi H.sub.2                                                                        Ti  °C.                                                                         Ratio gPE                                                                              KgPE/gTi                                                                            I.sub.2                                __________________________________________________________________________    1    24A  5    .0025                                                                             150   25   33.6                                                                             281   1.4                                    2    24A  5    .0025                                                                             185   25   37.5                                                                             313   2.9                                    3    24A  0    .0025                                                                             220   25   31.3                                                                             261   8.4                                    4    24B  5     .00125                                                                           150  100   37.9                                                                             633   10.9                                   5    24B  5    .0025                                                                             185  100   40.7                                                                             340   10.2                                   6    24B  0    .0025                                                                             220  100   17.6                                                                             147   8.1                                    __________________________________________________________________________

EXAMPLE 25

This example illustrates the use of tin tetrachloride as a halogenatingagent.

A. A catalyst slurry was prepared by mixing the following ingredients ina magnetically stirred bottle in the order listed:

12.5 ml--0.1 molar support solution prepared in Example 15a

69.7 ml--ISOPAR® G

12.5 ml--0.1 molar tin tetrachloride in ISOPAR® G

2.5 ml--0.01 molar tetraisopropyltitanate in ISOPAR® G

2.8 ml--0.892 molar triethylaluminum

B. A 10 ml aliquot of the catalyst prepared in section A was pressuredwith nitrogen into a stirred 1.8 liter stainless steel reactorcontaining 1.0 liters of ISOPAR® G, about 5 psi hydrogen, and 150 psiethylene at 150° C. The total reactor pressure was held constant byaddition of ethylene.

After 30 minutes of reaction, the reactor contents were dumped into a3.0 liter stainless steel resin kettle equipped with a reflux condensor.The solution was cooled to room temperature and the solvent removed. Thepolymer weighed 28.3 grams. The catalyst efficiency was 236,000 grams ofpolyethylene per gram of titanium. The polymer had a melt index of 0.41.

In order to broaden molecular weight distribution of produced slurrypolyxers, it is necessary that the Cl/Mg atomic ratio produced bytransition metal halides be less than about 0.5, the additional chlorinein the final catalyst obtained from an aluminum or boron compound, ormixtures of these, which chloride is added in a final chlorinating step.Thus, as described in this specification, at least 80% of the totalchloride in the final Cl/Mg ratio is obtained from aluminum or boronsources, or mixtures of these. It is preferred that even more of thetotal chloride be obtained from aluminum or boron (90% or more).

While certain embodiments and details have been shown for the purpose ofillustrating this invention, it will be apparent to those skilled inthis art that various changes and modifications may be made hereinwithout departing from the spirit or scope of the invention.

I claim:
 1. A method for preparing a hydrocarbon soluble magnesiumcompound having the general formula ##STR3## comprising contacting saidmaterial with sufficient organic ether to render a compound hydrocarbonsoluble, wherein the organic ethers have the general formula R² --O--R³,wherein R² and R³ can, optionally have mutual covalent bonds to formcyclic ethers, and wherein each of R, R², and R³ is, independently,alkyl groups containing from 1 to 20 carbon atoms, aryl, aralkyl, andalkaryl groups, each containing from 6 to 20 carbon atoms, and wherein Rcan, in addition, be hydrogen or alkoxy groups containing from 1 to 20carbon atoms, a is 0 or 1, and n is greater than
 0. 2. A method asdescribed in claim 1 wherein a is 0 and n is greater than
 0. 3. A methodfor preparing an olefin polymerization catalyst comprising(a) contactinga hydrocarbon insoluble magnesium compound of the general formula##STR4## with sufficient aluminum alkoxide and/or organic ethers torender the magnesium compound hydrocarbon soluble, wherein the aluminumalkoxides have the general formula Al(Q)₃, wherein each Q can be OR¹ orR¹, but at least one Q must be OR¹, and wherein the aluminum alkoxideand/or organic ethers are present at levels of from about 0.05 moles permole of magnesium to about 2 moles per mole of magnesium, based on theweight of the magnesium compounds present, and have the general formulaR² OR³, wherein R² and R³ can optionally have mutual covalent bonds toform cyclic ethers and wherein R, R¹, R², and R³, are, independently,alkyl groups containing from 1 to 20 carbon atoms, aryl, aralkyl, andalkaryl groups, each containing from 6 to 20 carbon atoms, R can also behydrogen or alkoxy groups containing from 1 to 20 carbon atoms, a is 0or 1 and n is greater than 0, with (b) non-halide transition metalalkoxides having at least one general formula

    MO.sub.g (OR.sup.4).sub.r

    R.sup.4 O[M(OR).sub.2 O].sub.p R.sup.4

    R.sup.4.sub.x M(OR.sup.4).sub.y

wherein M is titanium, vanadium, chromium or zirconium, each R⁴ is,independently, alkyl groups containing from 1 to 20 carbon atoms, arylgroups, alkaryl groups, and aralkyl groups each containing from 6 to 20carbon atoms, g is 0 or 1, r is 2 to 4, and 2g+r is equal to the valenceof M; p is at least 2; and x+y is equal to the valence of M to yield amagnesium to titanium ratio of at least 1:1, then (c) reacting themixture of (a) and (b) with a halogenating agent to obtain apolymerization catalyst having a halogen to magnesium ratio of at least2.0.
 4. A method as described in claim 3 wherein the non-halidetransistion metal alkoxide contains at least one material selected fromthe group consisting of tetraisopropyltitanate, tetra-n-butyltitanate,tetrabis(2-ethylhexyl) titanium, tri-n-butyl vanadate,tetra-n-propylzirconate and tetra-n-butylzirconate, iso--C₃ H₇--O[Ti(O--iso--C₃ H₇)₂ --O]₁₀ isoC₃ H₇, butyl (triisopropoxy) titaniumand mixtures thereof.
 5. A method as described in claim 4 wherein thehalogenating agent is a chlorinating agent.
 6. A method as described inclaim 5 wherein the chlorinating agent is at least one material selectedfrom the group consisting of ethylaluminum dichloride, diethylaluminumchloride, ethylaluminum sesquichloride, methyl and isobutyl analogs ofthese, tin tetrachloride, silicon tetrachloride, trichlorosilane,hydrogen chloride, aluminum chloride, ethylboron dichloride, boronchloride, diethylboron chloride, chloroform phosphorous trichloride,phosphorous oxytrichloride, acetyl chlorides, thionyl chloride, sulfurchloride, methyl trichlorosilane, dimethyl dichlorosilane, titaniumtetrachloride, vanadium oxytrichloride and vanadium tetrachloride.
 7. Amethod as described in claim 6 wherein the chlorinating agent isselected from the group consisting of diethylaluminum chloride,ethylaluminum dichloride and ethyl aluminum sesquihalide, methyl andisobutyl analogues of these.
 8. A method for preparing an olefinpolymerization catalyst comprising contacting a hydrocarbon insolublemagnesium compound of the general formula ##STR5## with an organic etherof the formula R² OR³ wherein R² and R³ can optionally have mutuallycovalent bonds to form cyclic ethers and R, R², and R₃ areindependently, alkyl groups containing from 1 to 20 carbon atoms, aryl,aralkyl, and alkaryl groups, each containing from 6 to 20 carbon atoms,R can also be hydrogen and alkoxy groups containing from 1 to 20 carbonatoms, a is 0 to 1 and n is from 0 to 100, wherein the resultingsolution is contacted with a transition metal halide to obtain apolymerization catalyst having a halogen to magnesium ratio of at least2.0.
 9. A method as described in claim 8 wherein n is greater than 0.10. A method as described in claim 9 when the transition metal halide istitanium tetrachloride and the organic ether is tetrahydrofuran.
 11. Amethod for preparing an olefin polymerization catalyst comprising(a)contacting a hydrocarbon insoluble magnesium compound of the generalformula ##STR6## with sufficient aluminum alkoxide and/or organic ethersto render the magnesium compound hydrocarbon soluble, wherein thealuminum alkoxides have the general formula Al(Q)₃, wherein each Q canbe OR¹ or R¹, but at least one Q must be OR¹, and wherein the aluminumalkoxide and/or organic ethers are present at levels of from about 0.05moles per mole of magnesium to about 2 moles per mole of magnesium,based on the weight of the magnesium compounds present, and have thegeneral formula R² OR³, wherein R² and R³ can optionally have mutualcovalent bonds to form cyclic ethers and wherein R, R¹, R², and R³, are,independently, alkyl groups containing from 1 to 20 carbon atoms, aryl,aralkyl, and alkaryl groups, each containing from 6 to 20 carbon atoms,R can also be hydrogen or alkoxy groups containing from 1 to 20 carbonatoms, a is 0 or 1 and n is greater than 0, with (b) sufficienthalogenating agent to obtain a halogen to magnesium ratio of at least2.0; and (c) reacting the mixture of (a) and (b) with non-halidetransition metal alkoxides having at least one general formula

    MO.sub.g (OR.sup.4).sub.r

    R.sup.4 O[M(OR).sub.2 O].sub.p R.sup.4

    R.sup.4.sub.x M(OR.sup.4).sub.y

wherein M is titanium, vanadium, chromium or zirconium, each R⁴ is,independently, alkyl groups containing from 1 to 20 carbon atoms, arylgroups, alkaryl groups, and aralkyl groups each containing from 6 to 20carbon atoms, g is 0 or 1, r is from 2 to 4, and 2g+r is equal to thevalence of M; p is at least 2; and x+y is equal to the valence of M toyield a magnesium to titanium ratio of at least 1:1 to obtain apolymerization catalyst.
 12. A method as described in claim 11 whereinthe non-halide transition metal alkoxide contains at least one materialselected from the group consisting of tetraisopropyltitanate,tetra-n-butyltitanate, tetrabis(2-ethylhexyl) titanium, tri-n-butylvanadate, tetra-n-propylzirconate and tetra-n-butyl zirconate, iso--C₃H₇ --O[Ti(O--iso--C₃ H₇)₂ --O]₁₀ iso C₃ H₇, butyl (triisopropoxy)titanium and mixtures thereof.
 13. A method as described in claim 12wherein the halogenating agent is a chlorinating agent.
 14. A method asdescribed in claim 13 wherein the chlorinating agent is at least onematerial selected from the group consisting of ethylaluminum dichloride,diethylaluminum chloride, ethylaluminum sesquichloride, methyl andisobutyl analogs of these, tin tetrachloride, silicon tetrachloride,trichloride, trichlorosilane, hydrogen chloride, aluminum chloride,ethylboron dichloride, boron chloride, diethylboron chloride, chloroformphosphorous trichloride, phosphorous oxytrichloride, acetyl chlorides,thionyl chloride, sulfur chloride, methyl trichlorosilane, dimethyldichlorosilane, titanium tetrachloride, vanadium oxytrichloride andvanadium tetrachloride.
 15. A method as described in claim 14 whereinthe chlorinating agent is selected from the group consisting ofdiethylaluminum chloride, ethylaluminum dichloride and ethyl aluminumsesquihalide, methyl and isobutyl analogs of these.
 16. A method forpreparing an olefin polymerization catalyst comprising(a) contacting ahydrocarbon insoluble magnesium compound of the general formula ##STR7##with sufficient aluminum alkoxide and/or organic ethers to render themagnesium compound hydrocarbon soluble, wherein the aluminum alkoxideshave the general formula Al(Q)₃, wherein each Q can be OR¹ or R¹, but atleast one Q must be OR¹, and wherein the aluminum alkoxide and/ororganic ethers are present at levels of from about 0.05 moles per moleof magnesium to about 2 moles per mole of magnesium, based on the weightof the magnesium compounds present, and have the general formula R² OR³,wherein R² and R³ can optionally have mutual covalent bonds to formcyclic ethers and R, R¹, R², and R³, are, independently, alkyl groupscontaining from 1 to 20 carbon atoms, aryl, aralkyl, and alkaryl groups,each containing from 6 to 20 carbon atoms, R can also be hydrogen oralkoxy groups containing from 1 to 20 carbon atoms, a is 0 or 1 and n isgreater than 0, with (b) a transition metal compound and a halidecompound, wherein the halide compound is a compound of boron oraluminum, and wherein the magnesium to titanium ratio is at least about5 to 1 respectively, then (c) react (a) and (b) with a halogenatingagent for form a polymerization catalyst having a halogen to magnesiumratio of at least 2.0, wherein only halogen obtained from compounds ofaluminum or boron or mixtures of these is used in determining thehalogen to magnesium ratio.